The Bodleian Library is facing a £400,000 bill from journal publishers as academics at the University of Oxford abandon print editions in favour of electronic access.
The charges have been incurred as a result of subscription cancellations at Oxford, as online access reduces the use of print journals across the institution.
As part of the bulk subscription packages negotiated with publishers, expenditure levels are agreed in advance by universities, including set thresholds for cancellations.
When the threshold is exceeded, penalty charges are incurred. As a result, the Bodleian has accrued a total of £400,000 in penalties in the past year alone.
A spokeswoman for the library said that the need for print editions had diminished as electronic access has become the norm among scholars.
She added that departmental and college libraries could save space and money by cancelling print subscriptions, many of which were duplicated in different parts of the university.
However, cancellations across the institution had resulted in expenditure dropping below the levels agreed in the contracts with publishers, leaving the Bodleian to pick up the bill.
"The cumulative and ongoing cost to the Bodleian has been substantial and although some extra income has been received from colleges and university funds, it does not cover the full cost," she said.
She warned that the charges meant that efforts to make savings in the Bodleian's acquisitions budget would have to come from non-journal resources.
She added that Oxford had incurred higher cancellation costs than any other UK university, and said that penalties would "continue to rise as more print subscriptions are cancelled".
Publishers that are already facing a number of challenges to their business models - not least from the move to open-access publishing in research - pointed out that such charges are simply part of the contracts they agreed with universities.
Eric Merkel-Sobotta, executive vice-president for corporate communications at Springer, said: "The multi-year licensing agreements that are signed allow for a single-digit percentage of subscriptions to be cancelled, allowing for flexibility.
"But other than that, subscribers are contractually bound by the agreements to continue to pay the terms that were agreed."
He added that high download rates by Oxford users meant that they were "getting good value out of their electronic products".
Mr Merkel-Sobotta said that one of the reasons why the Bodleian had been lumbered with such a large bill was Oxford's decentralised system of governance.
"The way that Oxford is organised is an anomaly: the Bodleian tries, but does not have a strong mandate to keep colleges and departments in line," he said.
A spokesman for the University of Cambridge said that it was not in the same position as Oxford, stating that no cancellation charges had been incurred by the Cambridge University Library.